EP3635019B1 - Polypropylene mit breiter molekulargewichtsverteilung und hohen schmelzflussraten und hohem biegemodul - Google Patents

Polypropylene mit breiter molekulargewichtsverteilung und hohen schmelzflussraten und hohem biegemodul Download PDF

Info

Publication number
EP3635019B1
EP3635019B1 EP18730483.7A EP18730483A EP3635019B1 EP 3635019 B1 EP3635019 B1 EP 3635019B1 EP 18730483 A EP18730483 A EP 18730483A EP 3635019 B1 EP3635019 B1 EP 3635019B1
Authority
EP
European Patent Office
Prior art keywords
polypropylene
reactor
catalyst
previous
polypropylenes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18730483.7A
Other languages
English (en)
French (fr)
Other versions
EP3635019A1 (de
Inventor
George J. Pehlert
David K. Brown
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of EP3635019A1 publication Critical patent/EP3635019A1/de
Application granted granted Critical
Publication of EP3635019B1 publication Critical patent/EP3635019B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04Monomers containing three or four carbon atoms
    • C08F110/06Propene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • C08F4/6465Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10Polymers of propylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/04Broad molecular weight distribution, i.e. Mw/Mn > 6
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12Melt flow index or melt flow ratio
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/02Ziegler natta catalyst

Definitions

  • the present invention relates to polypropylenes having a broad molecular weight distribution and high melt flow rate that maintain a high flexural modulus.
  • a polypropylene comprising within a range from 0 wt% to 4 wt% ethylene and/or C4 to C12 ⁇ -olefin derived units, having a melt flow rate (MFR, 230°C/2.16kg) greater than 20 g/10 min; an Mz/Mw of 4 to 7; a Mw/Mn of 14 to 22; and a flexural modulus of at least 250 (1720 MPa), or 280 (1930 MPa), or 300 kpsi (2070 MPa) (0.5 in/min ASTM D790(A)), wherein the polypropylene is reactor grade.
  • MFR melt flow rate
  • 230°C/2.16kg a
  • MFR melt flow rate
  • reactor grade polypropylenes comprising within a range from 0 wt% to 2, or 4 wt% ethylene and/or C4 to C12 ⁇ -olefin derived units, having:
  • the inventive polypropylenes can be described by any number of other features, and/or produced in a number of ways.
  • the polypropylenes have a number average molecular weight (Mn) of at least 10 kg/mole, or within a range from 10 to 35 kg/mole.
  • the polypropylenes have a weight average molecular weight (Mw) of at least 100 kg/mole, or within a range from 100, or 150 to 600, or 650, or 700, or 800 kg/mole.
  • the polypropylenes have a z-average molecular weight of at least 900, or 1000 kg/mole, or within a range from 900, or 1000 to 2,000, or 2,200, or 2,400, or 2,600 kg/mole.
  • the polypropylenes also have an Mw/Mn value within a range from 14 to 22. In any embodiment, the polypropylenes have an Mz/Mn value of greater than 4, or 10, or 20, or 50, or within a range from 4, or 10, or 20, or 50 to 110, or 120. In any embodiment, the polypropylene also has an Mz+1 value of at least 4,800, or 5,000 kg/mole, or within a range from 4,800, or 5,000 kg/mole to 6,000, or 6,500 kg/mole.
  • the Mz/Mw value for the polypropylene is within a range of 4, or 4.5 to 6.5, or 7 within an MFR range from 10, or 20 g/10 min to 100 g/10 min.
  • the polypropylenes may have certain desirable thermal properties as well.
  • the polypropylenes have a melting point temperature (T m ) of at least 156, or 158, or 160°C, or within a range from 156, or 158, or 160°C to 168, or 170, or 174°C.
  • T c crystallization temperature
  • the polypropylene has a heat deflection temperature (HDT) of at least 120, or 122°C, or within a range from 120, or 122°C to 130, or 134, or 140°C. These are the values without added nucleator.
  • HDT heat deflection temperature
  • the polypropylenes may have certain desirable structural properties.
  • the polypropylenes have an average meso run length (MRL) of 130, or 120, or 115 or less, or within a range from 85, or 90, or 95 to 115, or 120, or 130.
  • MRL average meso run length
  • the polypropylenes have 80, or 85, or 90 or more stereo defects per 10,000 monomers (Ds), or within a range from 80, or 85, or 90 to 115, or 120 defects/10,000 monomers.
  • the polypropylenes exhibit shear thinning.
  • the complex viscosity (logarithm) of the polypropylenes as a function of angular frequency applied to the melt at 190°C possess a nearly linear (negative slope) relationship, such as shown in FIG. 3 .
  • the polypropylenes possess a relatively high complex viscosity at very low frequencies (e.g., 0.01 rad/sec), but very low complex viscosity at high frequencies (e.g. 100 rad/sec).
  • the polypropylenes have a complex viscosity of less than 300, or 250 Pa•s, or within a range from 250 to 400, or 500 Pa•s at 100 rad/s (190°C).
  • polypropylenes have a complex viscosity of at least 2000, or 2500 Pa•s, or within a range from 2500, or 3000 Pa•s to 8000, or 10,000 Pa•s at 0.01 rad/s (190°C).
  • the polypropylenes can also be described by other mechanical properties.
  • the polypropylenes have an Izod impact of at least 0.2, or 0.3 ft-lb/in (23°C), or within a range from 0.2, or 0.3 to 1, or 1.2, or 2, or 2.4 ft-lb/in (23°C).
  • the polypropylenes may have a tensile strength at yield within a range from 34, or 36 MPa to 42, or 44, or 46, or 48 MPa.
  • the polypropylenes can be produced by any means of olefin polymerization, but are preferably produced from a single catalyst and single stage polymerization process.
  • single catalyst what is meant is that the olefins are contacted with a catalyst derived from the same or similar preparation, thus having the same or similar homogeneous composition such as a single Ziegler-Natta type of catalyst, metallocene catalyst, or other catalyst.
  • the single catalyst is a Ziegler-Natta catalyst with one or more external electron donors in a slurry polymerization system, preferably two external donors whose overall concentration can be varied, and/or they can be varied with respect to one another.
  • the single catalyst is a Ziegler-Natta catalyst that preferably includes a solid titanium catalyst component comprising titanium as well as magnesium, halogen, at least one non-aromatic "internal" electron donor, and at least one, preferably two or more "external” electron donors.
  • the solid titanium catalyst component also referred to as a Ziegler-Natta catalyst, can be prepared by contacting a magnesium compound, a titanium compound, and at least the internal electron donor.
  • the titanium compound used in the preparation of the solid titanium catalyst component include tetravalent titanium compounds having the formula Ti(OR n )X 4-n , wherein R is a hydrocarbyl radical, X is a halogen atom, and n is from 0 to 4.
  • a hydrocarbyl radical is defined to be C 1 to C 20 radicals, or C1 to C10 radicals, or C6 to C20 radicals, or C7 to C21 radicals that may be linear, branched, or cyclic where appropriate (aromatic or non-aromatic).
  • the halogen-containing titanium compound is a titanium tetrahalide, or titanium tetrachloride.
  • the magnesium compound to be used in the preparation of the solid titanium catalyst component includes a magnesium compound having reducibility and/or a magnesium compound having no reducibility. Suitable magnesium compounds having reducibility may, for example, be magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond.
  • Suitable examples of such reducible magnesium compounds include dimethyl magnesium, diethyl-magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, magnesium ethyl chloride, magnesium propyl chloride, magnesium butyl chloride, magnesium hexyl chloride, magnesium amyl chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and/or butyl magnesium halides.
  • the titanium-based Ziegler-Natta catalyst is said to be supported.
  • the Ziegler-Natta catalysts are used in combination with a co-catalyst, also referred to herein as a Ziegler-Natta co-catalyst.
  • a co-catalyst also referred to herein as a Ziegler-Natta co-catalyst.
  • Compounds containing at least one aluminum-carbon bond in the molecule may be utilized as the co-catalysts, also referred to herein as an organoaluminum co-catalyst.
  • organoaluminum compounds include complex alkylated compounds of metals of Group I of the Period Table (lithium, etc.) and aluminum represented by the general formula M 1 AlR 1 4 , wherein M 1 is the Group I metal such as Li, Na, or K, and R 1 is as defined in formula (2).
  • organoaluminum compounds include trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl-aluminum ethoxide and dibutyl aluminum ethoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui-butoxide.
  • trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum
  • trialkenyl aluminums such as triisoprenyl aluminum
  • dialkyl aluminum alkoxides such as diethyl-aluminum ethoxide and dibutyl aluminum ethoxide
  • alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui-butoxide.
  • Electron donors are present with the metal components described above in forming the catalyst suitable for producing the polypropylenes described herein. Both “internal” and “external” electron donors are desirable for forming the catalyst suitable for making the polypropylene described herein. More particularly, the internal electron donor may be used in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl. Examples of suitable internal electron donors include amines, amides, ethers, esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, and salts of organic acids.
  • the one or more internal donors are non-aromatic.
  • the non-aromatic internal electron donor may comprise an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioethers, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof.
  • the non-aromatic internal electron donor(s) comprises a C1 to C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid.
  • the external electron donors may comprise an organic silicon compound of the general formula R 1 n Si(OR 2 ) 4-n , wherein R 1 and R 2 independently represent a hydrocarbyl radical and n is 1, 2, or 3.
  • suitable organic silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diiso-propyldiethoxysilane, t-butylmethyl-n-diethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyl-dimethoxysilane,
  • the external electron donors are selected from any one or more of methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane cyclohexyltrimethoxysilane, tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltriethoxysilane, and/or dicyclopentyldimethoxysilane.
  • the production of the polypropylene preferably includes the use of two external electron donors, most preferably simultaneously. Suitable methods for using such external electron donors is disclosed in US 6,087,459 , and US 6,686,433 .
  • the two external electron donors may be selected from any of the external electron donors described herein.
  • the first external electron donor has the formula R 1 2 Si(OR 2 ) 2 , wherein each R 1 is independently a C1 to C10 hydrocarbyl radical in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a C1 to C10 hydrocarbyl radical; and the second external electron donor has the formula R 3 n Si(OR 4 ) 4-n , wherein each R 3 and R 4 are independently a C1 to C10 hydrocarbyl radical, and n is 1, 2, or 3; wherein the second external electron donor is different than the first external electron donor.
  • the combined concentration of external electron donors can be present with the catalyst and monomer(s) in the reactor to within a range from 10, or 20 ppm to 80, or 100, or 120 ppm.
  • the concentration of the catalyst system in the polymerization may be from 0.01 to 200 millimoles, or more preferably from 0.05 to 100 millimoles, calculated as a titanium atom, per liter of an inert hydrocarbon medium.
  • the organoaluminum co-catalyst may be present in an amount sufficient to produce from 0.1 to 500 g, or more preferably from 0.3 to 300 g, of a polymer per gram of the titanium catalyst present, and may be present at from 0.1 to 100 moles, or more preferably from 0.5 to 50 moles, per mole of the titanium atom present in the catalyst component.
  • suitable means of polymerization include contacting the catalyst and olefins in a gas phase reactor, stirred tank reactor, loop reactor, or other reactors known in the art.
  • the polymerization may take place in the gas phase, as a solution, or as a slurry.
  • hydrogen may be present in the reactor to modulate the molecular weight of the polypropylene being produced.
  • the hydrogen if combined with the single catalyst during the polymerization, is combined at a constant level. This means that the total concentration of hydrogen in the reactor is held constant (varying by no more than 1, or 2, or 3, or 5% of its overall level) during the production of the polypropylene.
  • the polymerization is most preferably a "single stage" polymerization process, meaning that the olefins and catalyst, and optional hydrogen are contacted under the same or similar conditions throughout the production of the polypropylene, such as in a single reactor, or multiple reactors in parallel or series, held at a constant level of temperature, pressure, monomer concentration, and hydrogen concentration, where no parameter changes by more than ⁇ 2%, or ⁇ 5%, or ⁇ 10% going from one reactor to another.
  • a polymerization is single stage even if performed in two or more loop slurry reactors in parallel if the reactor conditions are held at a constant level.
  • slurry polymerization process or “slurry polymerization reactor” refer to a process or reactor that handles polymer that is only partly dissolved or not dissolved at all in the medium, either monomer, solvent, or both, typically having at least 20 wt% polymer suspended or not dissolved.
  • catalyst components, solvent, monomers and hydrogen are passed under pressure to one or more polymerization reactors.
  • Catalyst components may be passed in the inventive processes to the polymerization reactor as a mixture in aliphatic hydrocarbon solvent, in oil, a mixture thereof, or as a dry powder.
  • the polymerization process is carried out using propylene as the only solvent.
  • the temperature of the reactor can be controlled by the rate of catalyst addition (rate of polymerization), the temperature of the solvent/monomer feed stream and/or the use of heat transfer systems.
  • reactor temperatures can range from 50 to 120°C or more, while pressures are generally higher than 300 psig, or within a range from 300 psig to 1000, or 1200 psig.
  • the polymerization temperature is preferably at least 50, or 60, or 70°C, or within a range from 50, or 60, or 70, or 80, or 90, or 100, or 120°C to 130, or 140, or 150, or 160, or 170°C.
  • the propylene and, if present, ethylene and/or other C4 to C12 ⁇ -olefins, are dissolved/dispersed in the solvent either prior to being passed to the polymerization reactor (or for gaseous monomers, the monomer may be passed to the reactor so that it will dissolve in the reaction mixture).
  • the solvent and monomers Prior to mixing, are generally purified to remove potential catalyst poisons.
  • the feedstock may be heated or cooled prior to delivery to the first reactor. Additional monomers and solvent may be added to the second reactor, and it may be heated or cooled.
  • the solvent is the propylene monomer itself.
  • the catalysts/activators can be passed to one polymerization reactor or split between two or more reactors. In solution or slurry polymerization, polymer produced is molten and remains dissolved or partially dissolved in the solvent under reactor conditions, forming a polymer solution.
  • the catalyst may be passed to the reactor in solid form or as a slurry/suspension in a solvent. Alternatively, the catalyst suspension may be premixed with the solvent in the feed stream for the polymerization reaction. Catalyst can be activated in-line, or by an activator with which it is co-supported. In some instances premixing is desirable to provide a reaction time for the catalyst components prior to entering the polymerization reactor, but this step is preferably absent.
  • the catalyst activity is preferably 20,000 kg polymer per kg of catalyst or more, more preferably 50,000 kg polymer per kg of catalyst or more, even more preferably 100,000 kg polymer per kg of catalyst or more.
  • the solution or slurry polymerization processes of this disclosure includes a stirred reactor system comprising one or more stirred polymerization reactors.
  • the reactors should be operated under conditions to achieve a thorough mixing of the reactants.
  • the reactors may operate at the same or different temperatures and fluidly connected in series, but preferably operate at the same temperature or within ⁇ 2°C of one another.
  • the residence time in each reactor will depend on the design and the capacity of the reactor.
  • the two or more reactors otherwise operate under the same conditions.
  • the solution or slurry polymerization process is carried out in one or more loop-type of reactors, preferably two fluidly connected in series.
  • reactor systems include a single reactor and multiple reactors in series or parallel configuration, such as that disclosed in US 2007/0022768 .
  • the solvent/monomer, preferably simply propylene, flow in these reactors is typically maintained using pumps and/or pressure systems, and may operate continuously by having monomer and catalyst feed at one point and extracting the forming polymer from another point, preferably downstream therefrom.
  • the conditions of temperature, catalyst concentration, hydrogen concentration, and monomer concentration may be the same or different in each loop reactor and may be tailored as necessary to suit the desired end product.
  • the solution polymerization process of this disclosure uses heat exchanger types of reactor where polymerization reaction takes place in the heat exchanger.
  • the reactors can be one or more shell and tube type of heat exchangers, or one or more spiral type of heat exchanger.
  • the polypropylene solution is then discharged from the reactor as an effluent stream and the polymerization reaction is quenched, typically with coordinating polar compounds, to prevent further polymerization.
  • the polymer solution On leaving the reactor system the polymer solution is passed through a heat exchanger system on route to a devolatilization system and polymer finishing process. Under certain conditions of temperature and pressure, the polymer solution can phase separate into a polymer lean phase and a polymer rich phase.
  • the polypropylene can be also recovered from the effluent by coagulation with a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer can be recovered by stripping the solvent or other media with heat or steam.
  • antioxidants can be incorporated in the polymer during the finishing procedure.
  • Possible antioxidants include phenyl-beta-naphthylamine; di-tert-butylhydroquinone, triphenyl phosphate, heptylated diphenylamine, 2,2'-methylene-bis(4-methyl-6-tert-butyl)phenol, and 2,2,4-trimethyl-6-phenyl-1,2-dihydroquinoline, and/or stabilizing agents such as tocopherols or lactones, or other agents as disclosed in WO 2009/007265 .
  • the inventive polypropylenes are "reactor grade” meaning that the polymers have not undergone any post-reactor process to change their chemical structure (e.g., cross-linking, branching, grafting), such as by reactive extrusion, electron-beam or ultra-violet radiation treatment, or silane grafting.
  • a polypropylene is "reactor grade” if for example no byproducts of peroxide reactions (visbreaking or cross-linking/long chain branch inducing) can be detected, and no grafted moieties are detected, and no long chain branching and/or cross-linked chains are detected.
  • Byproducts of peroxide reactions include alcohols and ketones and can be detected by NMR.
  • Long chain branching can be determined using the intrinsic viscosity (g'vis) of a polymer, which should have a value of less than 0.98, or 0.97, or 0.96 for a branched and/or cross-linked polypropylene.
  • the g'vis value for a polymer can be determined using a high temperature viscometer, in conjunction with GPC methods described further herein.
  • the polypropylene produced from a single catalyst and single stage polymerization process where preferably no other process has been carried out to alter the chemical structure of the polypropylene molecules.
  • the polypropylenes described herein may be subject to any number of post-reactor processing, such as reactive extrusion processes described in WO 2016/126429 A1 .
  • the polypropylene is combined with an organic peroxide, especially a short half-life peroxide in a melt extrusion process to produce a branched polypropylene, such polypropylenes typically having an enhanced melt strength and extensional viscosity.
  • this takes place in the absence of any additional monomers or cross-linking agents such as butadiene, 1,9-decadiene, norbornenes, or other diene-type monomers known in the art.
  • Useful organic peroxides include those that are short half-life peroxides such as di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dibutyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, didodecyl peroxydicarbonate, diicosyl peroxydicarbonate, and ditetracosyl peroxydicarbonate.
  • the polypropylene may be treated with a long half-life peroxide such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, di-tert-butyl peroxide, and dicumyl peroxide to effect "visbreaking" of the polypropylene as is known in the art.
  • a long half-life peroxide such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, di-tert-butyl peroxide, and dicumyl peroxide to effect "visbreaking" of the polypropylene as is known in the art.
  • the inventive polypropylenes find use in making many thermoformed articles such as automotive components, construction components, electronic devices, medical equipment, sports equipment, food containers, appliances, and other domestic and commercial uses.
  • the polypropylenes can find use thermoformed articles made from injection molding, blow molding, and rotational molding processes.
  • the polypropylenes described herein are useful in injection molding to form articles.
  • the injection molding process uses a ram or screw-type plunger to force molten polymer into a mold cavity; this solidifies into a shape that has conformed to the contour of the mold. It is most commonly used to process both thermoplastic and, thermosetting polymers, with the volume used of the former being considerably higher.
  • the inventive polypropylenes are useful due to characteristics which make them highly suitable for injection molding, such as the ease with which they may be recycled, their versatility allowing them to be used in a wide variety of applications, and their ability to soften and flow upon heating.
  • the temperature is preferably kept below the decomposition temperature of the polypropylene, preferably within a range from 140°C to 200, or 240°C.
  • thermoplastics such as the polypropylenes described herein also have an element of safety over thermosets; if a thermosetting polymer is not ejected from the injection barrel in a timely manner, chemical cross-linking may occur causing the screw and check valves to seize and potentially damaging the injection molding machine.
  • Injection molding consists of high pressure injection of the raw material into a mold which shapes the polymer into the desired shape. Molds can be of a single cavity or multiple cavities. In multiple cavity molds, each cavity can be identical and form the same parts or can be unique and form multiple different geometries during a single cycle.
  • thermoplastics such as the polypropylenes described herein are molded, typically pelletized material, preferably compounded with desirable additives such as antioxidants and alkyl-radical scavengers, is fed through a hopper into a heated barrel with a reciprocating screw. Upon entrance to the barrel the temperature increases and the molecular forces that resist relative flow of individual chains are weakened. This process reduces its viscosity, which enables the polymer to flow with the driving force of the injection unit.
  • the screw delivers the raw material forward, mixes and homogenizes the thermal and viscous distributions of the polymer, and reduces the required heating time by mechanically shearing the material and adding a significant amount of frictional heating to the polymer.
  • a “shot” is the volume of material that is used to fill the mold cavity, compensate for shrinkage, and provide a cushion (approximately 10% of the total shot volume, which remains in the barrel and prevents the screw from bottoming out) to transfer pressure from the screw to the mold cavity.
  • the process normally uses a transfer position corresponding to a 95 to 98% full cavity where the screw shifts from a constant velocity to a constant pressure control. Often injection times are well under 1 second.
  • the packing pressure is applied, which completes mold filling and compensates for thermal shrinkage, which is quite high for thermoplastics relative to many other materials.
  • the packing pressure is applied until the gate (cavity entrance) solidifies. Due to its small size, the gate is normally the first place to solidify through its entire thickness. Once the gate solidifies, no more material can enter the cavity.
  • the screw reciprocates and acquires material for the next cycle while the material within the mold cools so that it can be ejected and be dimensionally stable. This cooling duration can be reduced by the use of cooling lines circulating water or oil from an external temperature controller. Once the required temperature has been achieved, the mold opens and an array of pins, sleeves, strippers, etc. are driven forward to demold the article. Then, the mold closes and the process is repeated.
  • Injection molding is used to create many articles such as packaging, food containers, bottle caps, automotive parts and components, electronics casings, beauty care products, some musical instruments (and parts of them), one-piece chairs and small tables, storage containers, consumer goods containers for such items as moist wipes and food items, mechanical parts, and most other plastic articles available. Injection molding is ideal for producing high volumes of the same article.
  • Polypropylenes (hPP) having an Mz/Mw of at least 4 and an Mw/Mn of at least 10 (“BMW PP”) in a range of melt flow rates were produced in a stirred tank slurry polymerization reactor by contacting propylene, and optionally ethylene as stated in the final weight percentages in the tables below, with a Ziegler-Natta catalyst solid as described herein, triethylaluminum (TEAL), and propyltriethoxysilane and dicyclopentyldimethoxysilane as external donors, and hydrogen to a final MFR as stated in the tables.
  • the reactor was operated as a single stage in that the conditions of hydrogen, temperature, external electron donor, and pressure were constant.
  • Exemplary reactor conditions are as shown in Table 1.
  • Table 1. Suitable Loop-Slurry Polymerization Reactor Conditions 2 MFR hPP 25 MFR hPP 35 MFR hPP Donors (wppm in propylene) 30 30 30 TEAL (wppm in propylene) 50 50 50 50 H 2 concentration (mppm) 8,000 31,000 37,000 Reaction level (inches H 2 O) 16 16 16 Reaction residence time (hours, calculated) 1.7 1.7 1.7 reaction temperature (°C) 70 70 70 70 70 70 70 70
  • Reported and claimed values for Mn are ⁇ 2 kg/mole, for Mw are ⁇ 50 kg/mole, and for Mz are ⁇ 100 kg/mole.
  • Mw/Mn is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), while the “Mz/Mw” is the ratio of the Mw to the Mz, an indication of the amount of high molecular weight component to the polypropylene.
  • the Mw, Mn, and Mz values for the polypropylenes were determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10 ⁇ m Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 ⁇ m Teflon filter and degassed with an online degasser before entering the GPC instrument.
  • TCB 1,2,4-trichlorobenzene
  • BHT butylated hydroxytoluene
  • the nominal flow rate is 1.0 mL/min and the nominal injection volume is 200 ⁇ L.
  • the whole system including transfer lines, columns, detectors are contained in an oven maintained at 145°C.
  • Given amount of polymer sample is weighed and sealed in a standard vial with 80 ⁇ L flow marker (heptane) added to it.
  • polymer is automatically dissolved in the instrument with 8 mL added TCB solvent.
  • the polymer is dissolved at 160°C with continuous shaking for about 1 hour for most PE samples or 2 hour for PP samples.
  • the TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145°C.
  • the sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.
  • the conventional molecular weight (by infra-red detection) was determined by combining universal calibration relationship with the column calibration which was performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M g/mole.
  • the LS detector was a Wyatt Technology High Temperature Dawn Heleos.
  • ⁇ R( ⁇ ) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • "c” is the polymer concentration determined from the DRI analysis
  • a 2 is the second virial coefficient
  • P( ⁇ ) is the form factor for a mono-disperse random coil
  • Branching of a polypropylene is determined as follows.
  • a high temperature Viscotek Corporation viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, was used to determine specific viscosity.
  • One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity ( ⁇ s ) for the solution flowing through the viscometer was calculated from their outputs.
  • the polypropylenes were characterized using GPC, the results for which are summarized in Table 2. These are from a first set of experiments. Table 2. GPC Characteristics of the polypropylenes, non-nucleated Parameter 1 MFR BMW PP 2 MFR BMW PP 25 MFR BMW PP 43 MFR BMW PP 90 MFR BMW PP Mn (kg/mole) 26.6 26.0 16.8 13.8 11.3 Mw (kg/mole 536 491 259 219 181 Mz (kg/mole) 1,912 1,770 1,399 1,308 1,019 Mw/Mn 20.1 18.9 15.4 15.8 16 Mz/Mw 3.6 3.6 5.4 6.0 5.6
  • inventive polypropylenes were further characterized by other test methods. Some were nucleated with 1000 ppm sodium benzoate as indicated, otherwise were not. Two sets of experiments were performed, the first set in which the results are set forth in Table 3 (and Table 2), and the second set in which the results are set forth in Tables 4A to 4C. The "standard" commercial polypropylenes are plotted along with inventive polypropylenes from Table 3 in FIG. 1 . Blending studies with nucleators were carried out using a 57 mm extruder in the first set of experiments, and a 30 mm extruder in the second set.
  • the grades of polypropylene listed as "PP####" are all from ExxonMobil Chemical Company (Houston, Texas).
  • the “competitive HCPP1” is a commercial high crystallinity polypropylene homopolymer.
  • standard PP refers to a polypropylene homopolymer having a Mw/Mn value of less than 5, such as between 2.5 to 3.5.
  • DSC Differential Scanning Calorimetry
  • Sample sizes were from 3.5 mg to 5 mg and were heated at rate of 10°C/min from -20°C to 220°C in nitrogen gas flowing at a rate of 50 ml/min.
  • the samples were first cooled from 20°C to -20°C, then heated to 220°C to remove any thermal history. Then the samples were cooled from 220°C to -20°C, then heating back up from -20°C to 220°C in the second heating processes. All the DSC plots on first cooling and second heating were recorded.
  • the melting point temperature, T m was recorded during the second heating and is the peak heat flow (zero inflection), and the crystallization temperature, T c , was recorded during the first cooling at the peak minimum (zero inflection).
  • the Small Angle Oscillatory Spectroscopy was used to determine viscosity at low shear rates. Polymer samples were prepared using hot press (either a Carver Press or Wabash Press) to make disks of 25 mm in diameter and 2.5 mm in thickness. In order to characterize the shear thinning behavior, a rheometer ARES-G2 (TA Instruments) was used to conduct small angle oscillatory shear measurements at angular frequency ranging from 0.01 to 500 rad/s at temperature 190°C and at a fixed strain of 10%. The data was then converted into viscosity as a function of shear rate. To ensure that selected strain provides measurements within linear deformation range, the strain sweep measurements have been conducted (at angular frequency of 100 Hz). Data was processed using Trios software.
  • SAOS Small Angle Oscillatory Spectroscopy
  • stereo pentads Chemical shift assignments for the stereo defects (given as stereo pentads) can be found in the literature ( L. Resconi et al. in 100 CHEM. REv. 1253-1345 (2000 )).
  • the stereo pentads e.g., mmmm, mmmr, mrm, etc.
  • mm, mmmr and rr stereo triad distribution
  • m and r mole percentage diads
  • Three types of regio defects were quantified: 2,1-erythro, 2,1-threo and 3,1-insertion. The structures and peak assignments for these are also given in the reference by Resconi et al.
  • MRL 10,000/D total .
  • This definition of MRL is based upon the number of structural chain punctuations or defects that result from propylene insertions that have occurred in a non-regular fashion (stereo and regio defects). It does not include the punctuations due to the presence of comonomer (e.g., ethylene in a polypropylene random copolymer).
  • the regio defects each give rise to multiple peaks in the carbon NMR spectrum, and these are all integrated and averaged (to the extent that they are resolved from the other peaks in the spectrum), to improve the measurement accuracy.
  • the chemical shift offsets of the resolvable resonances used in the analysis are tabulated in US 7,807,769 .
  • HDT Heat deflection (distortion) temperature.
  • HDT was measured according to ASTM D648 using a load of 0.45 MPa (66 psi) or 1.8 MPa (264 psi) as designated.
  • Tensile Strength The tensile properties such as tensile strength at yield (also referred to here as yield stress) and elongation at yield (also referred to here as yield strain) were measured as per ASTM D638, with a crosshead speed of 50.8 mm/min (2.0 in/min) and a gauge length of 50.8 mm (2.0 in), using an Instron machine.
  • Izod Impact Strength The Izod impact of the polypropylenes and commercial examples was tested per ASTM D256.
  • Second set of inventive and commercial polypropylene Flexural Modulus measurements Sample Description 1% Sec Mod @ 0.05 in/min (kpsi) 1% Sec Mod @ 0.05 in/min (MPa) 1% Sec Mod @ 0.5 in/min (kpsi) 1% Sec Mod @ 0.5 in/min (MPa) BMW PP (20 MFR) 337 2320 376 2590 BMW PP (20 MFR) w/ NaBz 362 2500 399 2750 BMW PP (35 MFR) 323 2230 359 2480 BMW PP (35 MFR) w/ NaBz 357 2460 396 2730 Competitive HCPP1 333 2300 368 2540 ExxonMobil TM PP3155 205 1414 - - Table 4C.
  • Such additional additives can include, for example, fillers, nucleators or clarifiers, colorants, antioxidants, alkyl-radical scavengers (preferably vitamin E, or other tocopherols and/or tocotrienols), anti-UV agents, acid scavengers, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers (often referred to as hydrocarbon resins), and other additives well known in the art.
  • the phrase "consisting essentially of” means that there are no other process features that will alter the claimed properties of the polymer, polymer blend or article produced therefrom by any more than 10, 15 or 20%, but there may otherwise be minor process features not named.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • General Chemical & Material Sciences (AREA)

Claims (11)

  1. Polypropylen von Reaktorqualität, das innerhalb eines Bereichs von 0 Gew.-% bis 4 Gew.-% von Ethylen und/oder C4- bis C12-α-Olefin abgeleitete Einheiten umfasst, mit
    a) einer Schmelzflussrate (MFR, 230°C/2,16 kh) innerhalb eines Bereichs von 20 bis 500 g/10 min,
    b) einem Mz/Mw von 4 bis 7,
    c) einem Biegemodul von mindestens 250 kpi (1720 MPa) (0,5 in/min ASTM D790(A)),
    d) einem Mw/Mn-Wert von 14 bis 22.
  2. Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einem Mz+1-Wert von mindestens 4800 kg/Mol.
  3. Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer Schmelzpunkttemperatur (Tm) von mindestens 156°C.
  4. Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer Kristallisationstemperatur (Tc) von mindestens 116°C.
  5. Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer Wärmeformänderungstemperatur (HDT) von mindestens 120°C.
  6. Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer durchschnittlichen meso-Lauflänge (MRL) von 130 oder weniger.
  7. Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit 80 oder mehr Stereodefekten auf 10 000 Monomere (Ds) .
  8. Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer komplexen Viskosität von weniger als 300 Pa-s bei 100 rad/s (190°C) und/oder einer komplexen Viskosität von mindestens 2000 bei 0,01 rad/s Pa·s (190°C) und/oder einer Izod-Schlagfestigkeit von mindestens 0,2 ft·lb/in (23°C).
  9. Spritzgussartikel, der das Polypropylen von Reaktorqualität gemäß einem der vorhergehenden Ansprüche umfasst.
  10. Verfahren zur Herstellung von Polypropylen, das innerhalb eines Bereichs von 0 Gew.-% bis 4 Gew.-% von Ethylen und/oder C4- bis C12-alpha-Olefin abgeleitete Einheiten umfasst, bei dem Propylen und gegebenenfalls Ethylen und/oder C4- bis C12-al-pha-Olefine mit Einzelkatalysator, wobei der Einzelkatalysator ein Ziegler-Natta-Katalysator mit mindestens einem nicht-aromatischen internen Elektronendonor und einem oder mehreren externen Elektronendonoren ist, in einem einstufigen Polymerisationsverfahren in einem Aufschlämmungspolymerisationssystem kombiniert werden, und wobei Wasserstoff während der Polymerisation bei einem konstanten Niveau mit dem Katalysator kombiniert wird, wobei das resultierende Polypropylen eine Schmelzflussrate (MFR, 230°C/2, 16 kg) innerhalb eines Bereichs von 20 bis 500 g/10 min und einen Biegemodul von mindestens 250 kpsi (1720 MPa) (0,5 in/min ASTM D790(A)) aufweist.
  11. Verfahren nach Anspruch 10, bei der keine Nachreaktorverarbeitung des Polypropylens erfolgt, um die beanspruchten Eigenschaften zu erhalten.
EP18730483.7A 2017-06-07 2018-05-09 Polypropylene mit breiter molekulargewichtsverteilung und hohen schmelzflussraten und hohem biegemodul Active EP3635019B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762516145P 2017-06-07 2017-06-07
PCT/US2018/031804 WO2018226345A1 (en) 2017-06-07 2018-05-09 Broad molecular weight distribution polypropylenes with high melt flow rates and high flexural modulus

Publications (2)

Publication Number Publication Date
EP3635019A1 EP3635019A1 (de) 2020-04-15
EP3635019B1 true EP3635019B1 (de) 2023-10-25

Family

ID=62567741

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18730483.7A Active EP3635019B1 (de) 2017-06-07 2018-05-09 Polypropylene mit breiter molekulargewichtsverteilung und hohen schmelzflussraten und hohem biegemodul

Country Status (5)

Country Link
US (1) US11459453B2 (de)
EP (1) EP3635019B1 (de)
KR (1) KR102325239B1 (de)
CN (1) CN110914317B (de)
WO (1) WO2018226345A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI729874B (zh) * 2020-06-29 2021-06-01 臺灣塑膠工業股份有限公司 聚丙烯樹脂材料及其製作方法
WO2022035607A1 (en) 2020-08-11 2022-02-17 Exxonmobil Chemical Patents Inc. Face masks incorporating elastomeric layers and methods of producing such face masks
CN113214415B (zh) * 2021-04-20 2022-07-26 国家能源集团宁夏煤业有限责任公司 复合外给电子体、烯烃聚合催化剂及其应用以及聚烯烃及其制备方法
WO2023192461A1 (en) * 2022-04-01 2023-10-05 Chevron U.S.A. Inc. Process for stable blend of waste plastic with petroleum feed for feeding to oil refinery units and process of preparing same
US20240010927A1 (en) * 2022-07-08 2024-01-11 Chevron U.S.A. Inc. Blend of waste plastic with bio feed and process of preparation

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6686433B1 (en) 1994-02-04 2004-02-03 Exxonmobil Chemical Patents Inc. Dual donor catalyst system for the polymerization of olefins
WO1996011982A1 (en) 1994-10-12 1996-04-25 Kimberly-Clark Worldwide, Inc. Melt-extrudable thermoplastic polypropylene composition and nonwoven web prepared therefrom
CN1116315C (zh) * 1997-05-30 2003-07-30 株式会社宏大化纤 聚丙烯树脂组合物及注射成型制品
EP0942013B1 (de) 1997-08-05 2004-02-04 Mitsui Chemicals, Inc. Polypropylenharzzusammensetzung und deren verwendung
US6087459A (en) 1998-05-14 2000-07-11 Exxon Chemical Patents Inc. Polymeric materials formed using blends of electron donors
FI991057A0 (fi) 1999-05-07 1999-05-07 Borealis As Korkean jäykkyyden propeenipolymeerit ja menetelmä niiden valmistamiseksi
US6087750A (en) 1999-05-18 2000-07-11 Pacific Scientific Electro Kinetics Division Permanent magnet generator
US6809168B2 (en) 1999-12-10 2004-10-26 Exxonmobil Chemical Patents Inc. Articles formed from propylene diene copolymers
US7807769B2 (en) 2002-09-20 2010-10-05 Exxonmobil Chemical Patents Inc. Isotactic polypropylene produced from supercritical polymerization process
WO2005080497A1 (en) 2004-02-12 2005-09-01 Exxonmobil Chemical Patents Inc. Polypropylene resin suitable for fibers and nonwovens
US7678341B2 (en) 2005-07-29 2010-03-16 Exxonmobil Chemical Patents Inc. Loop reactor heat removal
ATE451421T1 (de) 2005-12-22 2009-12-15 Borealis Tech Oy Polypropylenzusammensetzung enthaltend ein propylenhomopolymer
WO2009007265A1 (en) 2007-07-10 2009-01-15 Basf Se Stabilizer compositions
EP2014707B1 (de) * 2007-07-12 2014-04-23 Borealis Technology Oy Modifizierte Polymerzusammensetzungen, Modifikationsverfahren und Wirkstoffe zur Erzeugung freier Radikale für I.A.-Draht und Kabelanwendungen
EP2386601B1 (de) 2010-05-11 2012-07-04 Borealis AG Langkettiges, verzweigtes Polypropylen mit hoher Fließfähigkeit
US9464178B2 (en) 2012-10-31 2016-10-11 Exxonmobil Chemical Patents Inc. Articles comprising broad molecular weight distribution polypropylene resins
WO2014070385A1 (en) * 2012-10-31 2014-05-08 Exxonmobil Chemical Patents Inc. Articles comprising broad molecular weight distribution polypropylene resins
JP6502530B2 (ja) 2015-02-04 2019-04-17 エクソンモービル ケミカル パテンツ インコーポレイテッド バランスのとれた歪み硬化、溶融強度、およびずり減粘を有するポリプロピレン
CN110785442B (zh) * 2017-05-30 2022-05-13 埃克森美孚化学专利公司 具有高劲度和透明度的高熔体强度聚丙烯

Also Published As

Publication number Publication date
KR20190142412A (ko) 2019-12-26
US20200172716A1 (en) 2020-06-04
KR102325239B1 (ko) 2021-11-10
CN110914317A (zh) 2020-03-24
EP3635019A1 (de) 2020-04-15
US11459453B2 (en) 2022-10-04
CN110914317B (zh) 2022-09-16
WO2018226345A1 (en) 2018-12-13

Similar Documents

Publication Publication Date Title
EP3635019B1 (de) Polypropylene mit breiter molekulargewichtsverteilung und hohen schmelzflussraten und hohem biegemodul
EP2283072B1 (de) Hochreine heterophasige propylencopolymere
EP2638109B1 (de) Verfahren zur herstellung von heterophasischen propylencopolymeren mit verbessertem steifheits-/stossfestigkeits-/fliessfähigkeitsverhältnis
EP1511803B1 (de) Propylen copolymerzusammensetzungen mit guter tieftemperatur-schlagfestigkeit und hoher transparenz
EP2527593B1 (de) Random Propylencopolymer mit hoher Steifigkeit und geringer Trübung
EP2638079B1 (de) Verbessertes verfahren zur herstellung heterophasischer propylencopolymere
RU2662152C2 (ru) Пропилен-этиленовые статистические сополимеры и способ их получения
KR20080087082A (ko) 프로필렌 공중합체 성분을 포함하는 폴리프로필렌 조성물
EP2452975A1 (de) Weiche heterophasische Propylencopolymere
CN105264007A (zh) 用于管材应用的多峰聚丙烯组合物
EP2062937A1 (de) Heterophasiges Propylencopolymer für Wellbleche und gegossene Filmanwendungen
EP2743307A1 (de) Polyolefinzusammensetzung
EP3580275B1 (de) Polypropylen mit hoher schmelzfestigkeit mit verbesserter verarbeitbarkeit
EP2719725A1 (de) Nukleierte Polypropylenzusammensetzung für Behälter
WO2018025864A1 (ja) ヘテロファジックプロピレン重合材料の製造方法
EP2796472A1 (de) Zweistufiges Verfahren zur Herstellung von Polypropylenzusammensetzungen
EP2452959B1 (de) Verfahren zur Herstellung von statistischen Propylencopolymeren und deren Verwendung
US11549006B2 (en) High melt strength polypropylene with high stiffness and clarity
EP3877464B1 (de) Polyolefinzusammensetzung mit verbesserter schlag- und aufhellungsbeständigkeit
EP2216350B1 (de) Polypropylenzusammensetzung mit hoher Steifigkeit und Stoßfestigkeit
EP2398830B1 (de) Verbreiterung der molekulargewichtsverteilung von in einem horizontalen gerührten gasphasenreaktor hergestellten polyolefinmaterialien
JP2017036390A (ja) プロピレン系樹脂組成物および成形体
CN110183782A (zh) 一种双无规抗冲共聚聚丙烯材料及其工业化生产方法
WO2018147944A1 (en) High melt strength polypropylenes with improved processability
EP3885376A1 (de) Verfahren zur herstellung eines propylenpolymers

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191220

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20220218

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230512

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230803

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018059944

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20231025

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1624591

Country of ref document: AT

Kind code of ref document: T

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240225

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240126

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240125

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240125

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240521

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240529

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025